Oil-soluble metal sulfonates and process for the preparation thereof



United States Patent OIL-SOLUBLE CMETAL SUIJFONATES AND PROC- 'ESS FOR THE PREPARATION THEREOF William M. Le Suer, Cleveland, Ohio, assignor to The Lubrizol Corporation, Wicklilfe, Ohio, a corporation of Ohio No Drawing. Application May 8, 1957 Serial No. 657,737

Claims. (Cl. 260-139) This invention relates to novel compositions and to methods for the preparation of same. In a more particular consideration it relates to a method of sulfonation and the subsequent modification of the sulfonated products thereof.

This application is a continuation-in-part of my application Ser. No. 466,237, filed November 1, 1954, and now abandoned.

The commercial use of organic sulfonates has increased at a rapid rate in the last several years. Among the factors entering into this increased use has been the particular utility of these sulfonates, either per se in lubricants or in the preparation of other detergents for use in lubricants. The performance characteristics of sulfonates in mineral lubricating compositions has been such that they comprise a very large proportion of all detergents which are so used. With the wide popular acceptance of heavy duty motor oils which contain large amounts of detergents it will be seen that this is indeed a considerable factor.

As is so often the case in such situations where a commodity is suddenly in great and increasing demand the organic sulfonates have frequently been in critically short supply and there has been much effort directed to the problem of increasing or extending this supply.

It is accordingly a principal object of this invention to provide a process by means of which the supply of organic sulfonates can be extended.

It is also an object of the present invention to provide a process for the preparation of novel derivatives of sulfonic acids.

It is still further an object of this invention to provide lubricating compositions which contain the above novel compositions dispersed therein.

Other objects will be apparent from the following description.

The above objects are accomplished by the process of preparing oil-soluble alkaline earth metal sulfonates containing relatively large amounts of metal, which comprises the reaction of a neutral oil-soluble metal salt with a sulfonating agent to form an acidic metal salt, and subsequent treatment of said acidic metal salt with a stoichiometrically excessive amount of an inorganic, basically reacting alkaline earth metal compound in the presence of a promoter selected from the class consisting of phenolic compounds and alcohols.

The utility of the above process is particularly evident in an overall preparation of oil-soluble metal sulfonates according to this method. By means of this process the quantity of oil-soluble sulfonates available from a given quantity of petroleum or other alkylated aromatic material may be considerably increased over thatvwhich is available merely from the sulfonation of this same petroleum-or alkylated aromatic material. An explanation of this phenomenon is not readily discernible. It may be that the molecules which contain sulfonate groups are sulfonated again and that-the presence in the reaction mixture of a dispersing agent such as the metal sulfonates is sufiicient to retain these sulfonate-sulfonic acids in oil solution. Or it may be that the unsulfonated hydrocarbons present in the metal sulfonate solutions are sulfonated.

The oil-soluble metal salts which comprise the raw material for this process are principally the metal sulfonates and the metal salts of polyolefin-phosphorus pentasulfide condensation products and their derivatives. Such sulfonates include not only the mahogany sulfonates but also the sulfonates of synthetic alkylated aromatic hydrocarbons such as dodecyl-benzene sulfonates, etc..

The polyolefin-phosphorus pentasulfide condensation products are described in U.S. Patents 2,316,078; 2,316,091; 2,367,468; 2,375,315; 2,377,955; 2,496,508; 2,507,731; 2,597,750; 2,647,889. They comprise preferably the salts of such condensation products which have been treated with steam, either before or after neutralization, so as to remove some of the sulfur and to produce thereby a more desirable product, particularly as regards odor.

The alkaline earth metal constituent of these oil-soluble metal salts include barium, calcium, and strontium as well as mixtures thereof.

Specific examples of oil-soluble metal salts include the following: sodium mahogany sulfonate, sodium dodecyl benzene sulfonate, sodium salt of a steam-treated phosphosulfurized polyisobutylene, potassium mahogany sulfonate, lithium salt of a phosphosulfurized polyisobutylene, calcium dodecyl benzene sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, barium salt of a phosphosulfurized polyisobutylene, magnesium dodecyl benzene sulfonate, etc.

The sulfonating agent used in the process may be any of the ordinarily used sulfonating materials, viz., oleum, concentrated sulfuric acid, sulfur trioxide, chlorosulfonic acid, the various complexes of sulfur trioxide, etc. Of

these, for reasons of economy and convenience of reaction, it is preferred to use chlorosulfonic acid.

In view of the exothermic nature of the reactionof the process it is advisable to carry out the process by adding one of the reactants to the other in a portionwise fashion. A particularly convenient method is the portionwise addition of the sulfonating agent to the oil-soluble metal salt, or to a solution of the metal salt. The temperature of the sulfonation is conveniently within the range of 0-200 C. Preferably the temperature is maintained at some relatively constant temperature between 25 C and C. As indicated previously, the sulfonation exothermic and little or no additional heat is required to maintain a temperature of, for example 60-80.

When chlorosulfonic acid is used as the sulfonating agent the sulfonation reaction is accompanied by a copious evolution of hydrogen chloride, and because of the tendency for some of this evolved hydrogen chloride to remain dissolved in the reaction mixture, it is advisable to flush the sulfonation mass with some inert gas, such as nitrogen, etc.

The product directly obtainable from the sulfonation of an oil-soluble metal salt is an acidic material and as such is of value as an intermediate in the preparation of normal and basic metal salts. The preparation of a basic salt can be accomplished by any of several methods previously disclosed in U.S. 2,501,731; 2,402,325; 2,485} 861; 2,616,924; 2,617,049; 2,619,460; as well as in copending application, U.S. Serial No. 483,177, filed Jan: uary 20, 1955. Thus the acidic product which is available from the process of this invention may be treated with the stoichiometric amount of a basically reacting metal compound required to produce the normal salt, or it may be so treated with more than this amount in which case a basic metal salt will be obtained. In the latter case the incorporation into the product of metal in excess of the stoichiometric amount required to neutralize the acidity of the sulfonation product may be assisted by promoters, high temperature, etc. as disclosed in the previously mentioned patents.

As basically reacting metal compounds which may be used to prepare either the normal or basic salts it is preferred touse oil-insoluble metal compounds. These include principally the inorganic compounds such as the oxides, hydroxides, carbonates, etc. and the lower molecular weight alcoholates such as methylates, butylates, etc. Of these particular preference exists for the inorganic, basically reacting metal compounds.

Other valuable products which may be formed from these acidic sulfonate salts include the neutral compositions which contain considerably more metal than that required merely to neutralize the acidity of the sulfonated salts. Such neutral compositions may be obtained by treating the acidic sulfonated salt with a stoichiometric excess of a metal oxide or' hydroxide and then treating this basic mass with an acidic gas such as carbon dioxide, sulfur dioxide, hydrogen sulfide, etc. This latter process may be carried out in the presence of a promoter such as a tautomeric compound (phenols, enols, aci-nitro compounds, etc.) as disclosed in the previously mentioned patents, or an alcohol.

In this latter instance, i.e., where such a basic mass contains a tautomeric promoter it will be desirable to use an acidic gas which has an ionization constant greater than that of the promoter.

Tautomeric promoters include principally the phenolic materials having an ionization constant in water of at least 1X10" at 25 C., a water solubility of at least about 0.0005 percent at 50 C., and in a saturated aqueous solution at 25 C., a pH of less than 7.

For the purpose of the present specification and appended claims, the term metal ratio is the ratio of total equivalents of metal in the composition to equivalents of high molecular weight organic acid present therein. Thus, for example, a normal metal sulfonate would have a metal ratio of 1.0 whereas a basic sulfonate of the type RSO MOH would have a metal ratio of 2.0. Thus the term metal ratio is a convenient and quantitative way of expressing the amount of excess metal present in the composition.

The invention is illustrated in greater detail by the following examples.

Example 1 A mixture of 4200 grams (5.6 equivalents) of polyisobutylene having an average molecular weight of 750 and 394 grams (12.3 equivalents) of sulfur was heated to 170 C. with stirring. To this mixture there was added portionwise throughout a period of 3.5 hours 847 grams (6.2 equivalents) of phosphorus trichloride. The phosphorus trichloride was added beneath the surface of the reaction mixture. The temperature then was raised to 195 C. and held at this level for an additional hour. The product mixture was diluted with 1000 grams of white oil and then treated with steam for 2 hours at ISO-170 C. After another hour of heating at this temperature the product was diluted further with 1100 grams of mineral oil.

To a mixture of 2060 grams (2.0 equivalents) of the above product, 1200 grams of mineral oil and 175 grams of water there was added at 70 C. 153 grams (2.0 equivalents) of barium oxide. This mixture was heated at reflux for one hour then freed of water by raising the temperature to 150 C. After 2 hours of heating at this latter temperature the mixture was allowed to cool to 70 C. whereupon 233 grams (2.0 equivalents) of chlorosulfonic acid was added portionwise. The sulfonation mixture then was flushed with nitrogen for 2 hours.

Amixture of'492 grams (2.4 equivalents) of heptyl phenol, 1942 grams of mineral oil and 38 m1. of water was addedto the above product-and the resulting mixture heated to 70 C. To this was added 1358 grams (mak- Percent sulfur 1.2

Basic No. 0.9

Percent sulfate ash 28.3

Metal ratio 4.8

Example 2 To 1192 grams (1.0 equivalent) of a 40% oil solution of mixed barium petroleum sulfonate and barium dodecyl benzene sulfonate analyzing 10.0% sulfate ash there was added at 6070 C. 122 grams (1.05 equivalents) of chlorosulfonic acid. The. resulting reaction was exothermic. When all the chlorosulfonic acid had been added the mixture was stirred for an additional fifteen minutes and then flushed with nitrogen for one hour. This liquid product, having an acid number of 57 then was treated with 520 grams (1.2 equivalents) of a diisobutylphenol-formaldehyde condensation product (in which one mole of the phenol was condensed with 0.38 mole of formaldehyde), 965 grams of mineral oil, grams of water and 680 grams (8.9 equivalents) of barium oxide. This mixture was heated with stirring for one hour at 100105 C. and then for an additional hour at ISO-160 C. The mixture then was filtered through a siliceous filter aid to yield an oil-insoluble product having the following analyses:

Percent sulfur 2.0

Basic No. 38

Percent sulfate ash 20.8

Metal ratio 3.2

Example 3 To 1165 grams (1.0 equivalent) of a 40% oil solution of barium dodecyl benzene sulfonate there was added dropwise at 60-70 C. 122grarns (1.05 equivalents) of chlorosulfonic acid. The product mixture then was flushed for two hours with nitrogen and then treated with 520 grams (1.2 equivalents) of the diisobutylphenolformaldehyde condensation product of Example 2, 990 grams of mineral oil, 680 grams (8.9 equivalents) of barium oxide and 360 grams of water. This mixture was heated for one hour at 100-105? C.; heated'to C. and then treated at this temperature with carbon dioxide until the mixture was substantially neutral. A silicious filter aid was added'and the mixture-was filtered to yield a clear, oil-soluble product having the following analyses:

Percent sulfur 1.8

Basic No 7.7

Percent sulfate ash 30 Metal ratio 4.7

Example 4 A 60% oil solution weighing 660 grams (1.0 equivalent) of sodium dodecyl benzene sulfonate was diluted with 300 grams of mineral oil and then treated at 60-70" C. with 116.5 grams (1.0 equivalent) of chlorosulfonic acid. This mixture was flushed with nitrogen for one hour, at which point the acid number of the solution was 65. Tothis acidic solution there was added 329 grams (1.2 equivalents) of the diisobutylphenol-formah dehyde condensation product of Example 2, 800 grams of oil, 300 grams of water and then, portionwise, 678" grams (8.9 equivalents) of barium oxide; The resulting mixture washeated'for' one hour at 100-105 C'., then to 150 (3. at which temperature it was treated with carbon dioxide until substantially neutral. A further one-hour period of heating at ISO-160 C. was followed by filtration through a siliceous filter aid to yield an oilsoluble product having the following analyses:

Example 5 To 1642 grams (1.0 equivalent) of the barium salt of a phosphorusand sulfur-containing acid (prepared by steam treatment of a polyisobutylene (M.W.- 750)- P S condensation product) there was added at 6070 C. 116.5 grams (1.0 equivalent) of chlorosulfonic acid. The resulting mixture was heated for one hour at 60- 70 C. in an atmosphere of nitrogen. To this product there was added 329 grams (1.2 equivalents) of diisobutylphenol-formaldehyde condensation product of Example 2, 680 grams (8.9 equivalents) of barium oxide; 1106 grams of mineral oil and 100 grams of water. This mixture was heated with stirring for one hour at 100- 105 C. and then for an additional hour at 150160 C. The product was filtered through a siliceous filter aid to yield a clear oil-soluble liquid with the following analyses:

Percent sulfur 1.1

An acidic product having an acid number of 56 was prepared as in Example 2. To this was added 1480 grams of mineral oil, 200 grams of methanol and slightly more than the theoretical amount of barium oxide required to neutralize the acidity of the mixture. Carbon dioxide was then bubbled into the mixture and an additional amount of barium oxide, such that the total amount used was 383 grams (5.0 equivalents), was added portionwise at reflux temperature. The mixture was treated with carbon dioxide until substantially neutral and then dried by heating at ISO-160 C. Filtration through a siliceous filter aid yielded a clear oil-soluble product with the following analyses:

Percent sulfur 2.1

Acid No 0.2

Percent sulfate ash 20.9

Metal ratio 2.8

Example 7 at ISO-160 C. untilit was approximately neutral. The carbonated mass then was dried and filtered/through a siliceous filter aid to yield a clear, oil-soluble liquid product with the following analyses:

Percent sulfur 1.2 Basic No 4.1 Percent sulfate ash 30.0

Metal ratio 4.7

Example 8 A solution of 4000 grams (5.3 equivalents) of polyisobutylene having an average molecular weight of 750, in 1000 ml. of ethylene dichloride and 1000 ml. of lactol spirits was treated at 2842 C. throughout a period of 3.5 hours with 1865 grams (16.0 equivalents) of chlorosulfonic acid. The resulting mixture was stirred for 2 hours then washed with ice water. The dried product (2280 grams, 2.0 equivalents) was mixed with 1260 grams of mineral oil and 180 ml. of water and heated to 70 C. To this mixture there was added 153 grams (2.0 equivalents) of barium oxide and the resulting mixture heated at reflux temperature for an hour. This'mixture was dehydrated by heating to 150 C., then cooled to C. and treated portionwise throughout a -minute period with 233 grams (2.0 equivalents) of chlorosulfonic acid. Nitrogen was bubbled through this product at 80 C. for 2 hours whereupon 4428 grams of mineral oil, 246 grams 1.2 equivalents) of heptyl phenol and 160 ml. of Water were added. This mixture in turn was heated to 70 C., 1359 grams (17.7 equivalents) of barium oxide added, and the whole heated at reflux temperature for an hour. The temperature was raised to 150 C. and carbon dioxide bubbled therethrough until the mixture was slightly acidic. Filtration through a siliceous filter aid yielded a clear oil-soluble filtrate having the following analyses:

Percentsulfur 1.1

Basic No 2.0

Percent sulfate ash 21.2

Metal ratio 4.5

Example 9 To 876 grams (0.4 equivalent) of a chlorosulfonated barium salt prepared as in Example 5 there was added 1125 grams of mineral oil, ml. of water and 246 grams (4.8 equivalents) of strontium oxide. This mixture was stirred for hour then treated with 894 grams (9.5 equivalents) of phenol. This mixture was heated at reflux temperature for 2 hours, dried by heating to C., then treated with carbon dioxide until the mixture was slightly acidic. Filtration through a siliceous filter aid and dilution of the filtrate with mineral oil yielded a product having the following analyses:

Percent sulfur 0.6 Basic No. 3.0 Percent barium 0.7 Percent strontium I 3.4

Metal ratio 2.7

Example 10 T0874 grams (0.4 equivalent) of a chlorosulfonated barium salt prepared as in Example 5 there was added 1125 grams of mineral oil, 200 ml. of water and 246 grams (4.8 equivalents) of strontium oxide. To this stirred mixture there was added 200 grams (3.2 equivalents) of ethylene glycol and the resulting mixture heated at reflux temperature for one hour. The mixture was dehydrated by raising the temperature to 150 C. whereupon carbon dioxide was bubbled through the mixture until it was acidic. The acidified product was filtered through a siliceous filter aid and then concentrated by heating to a final temperature of 210 C./ 10 mm. The

Example 11 To 757 grams (0.4 equivalent) of a chlorosulfonated barium 's'alt prepared as in Example 5 there was added 864 grams of mineral oil, 90 ml. of water, 158 grams (4.3 equivalents) of calcium hydroxide and 805 grams (8.6 equivalents) of phenol. The resulting mixture was heated at reflux temperature for one hour then dried by raising the temperature to 150 C. This dried mixture was carbonated until it was slightly acidic and then concentrated by distilling 697 grams of phenol from the mixture. The residue was diluted with 50 grams of iso-octyl alcohol to yield to product having the following analyses:

Percent sulfur 0.8 Basic No. 5.0 Percent barium 1.5 Percent calcium 0.6 Metal ratio 4.2

Example 12 To 14,940 grams (20.0 equivalents) of polyisobutylene having an average molecular weight of 750 there was added at 260 C. 2199 grams '(9.9 equivalents) of phosphorus pentasulfide. The phosphorus pentasulfide was added portionwise over a period of 6 hours and the mixture was maintained to 260 C. for an additional 2 hours. This reaction mixture was treated with 1080 grams (60 equivalents) of steam at 162 C. The resulting product was filtered through a siliceous filter aid.

A mixture of 685 grams (0.8 equivalent) of the above acidic product, 500 grams of mineral oil and 30 ml. of water was heated to 70 C. and treated portionwise with 56 grams (1.5 equivalents) of calcium hydroxide. This mixture was heated at reflux temperature for an hour and then dried by raising the temperature to 150 C. The dried product was filtered through a siliceous filter aid. To a solution of 300 grams (0.2 equivalent) of the filtrate in 300 grams of mineral oil at 70 C. there was added portionwise throughout a 30-minute period 29 grams (0.25 equivalent) of chlorosulfonic acid. When the ensuing reaction had subsided the unreacted chlorosulfonic acid was decomposed with water and 88 grams (2.4 equivalents) of calcium hydroxide and 445 grams (4.8 equivalents) of phenol were added. The resulting mixture was heated to 150 C. and treated with carbon dioxide until it was acidic. To this carbonated product there was added another 159 grams of mineral oil and 63 grams of iso-octyl alcohol. The mixture was filtered to yield a clear liquid product having the following analyses:

Percent sulfur 0.7

To 685 grams (0.8 equivalent) of the acidic reaction product of polyisobutylene and phosphorus pentasulfide prepared in Example 12 there was added 500 grams of mineral oil, 30 ml. of water and 78 grams (1.5 equivalents) of strontium oxide. This mixture was heated at reflux temperature for one hour then diluted further with another 300 grams of mineral oil. Water was removed by raising the temperature to 150 C. and the residue was filtered through a siliceous filter aid. To 383 grams (0.2 equivalent) of this normal strontium salt (the filtrate) there was added 300 grams of mineral oil and then at 70 C., 29 grams (0.25 equivalent) of chlorosulfonic acid. The chlorosulfonic acid was added drop- Wise over a period of 30 minutes, the temperature being maintained at 70-80 C. Nitrogen was bubbled through the product mixture for 2 hours. The product was diluted further with another 300 grams of mineral oil and then mixed with 50 ml. of water and 123 grams (2.4 equivalents) of strontium oxide. The mixture was stirred for 15 minutes then treated with 445 grams (4.8 equivalents) of phenol. Water was removed by raising Percent sulfur 0.8

Basic No. 5.0

Percent strontium 7.9

Metal ratio 4.6

Example 14 A chlorosulfonated normal strontium salt was prepared as in Example 13 and treated with 123 grams (2.4 equivalents) of strontium oxide and 200 grams (6.5 equivalents) of ethylene glycol. This mixture was heated at reflux temperature for one hour, then dried by raising the temperature to C. whereupon carbon dioxide was bubbled through the mixture until it was slightly acidic. The carbonated product was diluted with 300 grams of mineral oil, then filtered through a siliceous filter aid. The filtrate was concentrated by heating to a final temperature of C./l0 mm. The residue showed the following analyses:

Percent sulfur 0.8 Acid No. 0.4 Percent strontium 5.9 Metal ratio 3.2

The utility of the detergent compositions which can be prepared from the acidic sulfonated salts of this invention is apparent from results of engine test data gathered from work with crankcase lubricants containing these detergent compositions. One such engine test is an adaptation of the L-l Engine Test, CRC Designation L-1-545, and involves operation of a one-cylinder, 4-cycle, diesel engine under certain specified conditions for a long period of time. In the otficial description of this test there appears the following:

Sc0pe.(1) This procedure is intended for determining the effect of engine oils on ring-sticking wear, and the accumulation of deposits under endurance conditions. While the test is carried out in a compression-ignition engine of the high-speed type, experience has shown that this procedure also correctly evaluates oils for use in heavy-duty spark-ignition automotive engines.

This procedure will evaluate the following qualities of engine oils under endurance test conditions:

((1) The tendency of the engine oil to form materials in the ring grooves which bind the rings and prevent their free action, resulting in ring-sticking.

(b) The tendency of the engine oil to form excessive lacquer deposits on the piston resulting in improper heat transfer.

(0) The tendency of the engine oil to form deposits at the top of the cylinder which cause piston crown scufiing.

((1) The efliciency of the engine oil in reducing piston ring and cylinder wear.

The adaptation of the test conditions involves the use of fuel which contains one percent sulfur. This latter variation makes theprocedure a considerably critical test as regards detergency since sulfur-containing fuels contribute seriously to the formation of lacquer and varnish deposits.

The results of such a test are determined by visual inspecting of the piston, rings, etc. as follows:

(1) Percentage of the volume of the oil ring groove which is occupied by deposits.

(2) Overall cleanliness of the ring-belt area of the piston; i.e., the portion of the piston below the oil ring groove (100 meaning perfectly clean).

The following data show the results of such engine tests in which the lubricant comprised a mid-continent SAE 30 oil containing 0.5% by weight of a zinc dialkyl phosphorodithioate inhibitor plus the indicated amounts of the products of this invention:

A similar detergency test for lubricants involves the use of a Buda diesel engine. Again the fuel used is one which contains one percent sulfur so as to place a heavy burden on the detergent of the lubricant being tested.

The rating given to a lubricant which is subjected to this test comprises an overall piston cleanliness score (100 being perfectly clean) and a percentage estimate of the degree to which the volume of the top ring groove is filled with deposits.

The following data shows the results of such Buda diesel tests in which the lubricants tested comprised a midcontinent SAE 30 oil plus 0.5% by weight of a zinc dialkyl phosphorodithioate inhibitor plus the indicated amounts of the products of this invention:

Overall Top ring Hours piston groove cleanlideposits, ness percent 0. 0.63% sulfate ash as the product of Example 1 150 91. 2 D. 0.67% sulfate ash as the product of Example 2 150 81.5 16 E. 1.0% sulfate ash as the product of Example 2 150 91.0 2 F. 0.5% sulfate ash as the product of Example 6 150 97. 1 G. 0.67% sulfate ash as the product of Example 8 150 85. 0 1 H. 0.8% sulfate ash as the product of Example 13 150 95.0 1

A lubricant consisting of a mid-continent SAE 30 oil plus 0.5% by weight of a zinc dialkyl phosphorodithioate inhibitor showed an overall piston cleanliness of 37 and a top ring groove deposit rating of 60% when subjected to the conditions of this test. The motor oil detergents which can be prepared from the products of the hereindescribed process may be used in lubricating compositions within the range of concentration of 0.003 to 8.0 percent sulfate ash, and it is preferred to use concentrations within the range of 0.01 to 4.0 percent sulfate ash. It will be appreciated that the term sulfate ash provides a more equitable basis upon which to define the effective amounts of a detergent-type additive since the activity of a motor oil detergent is believed to be related to the amount of metal present in the oil. The sulfate ash analysis of a substance is an indirect measure of the metal content thereof.

The use of concentrated solutions of the hereindescribed motor oil detergents allows a convenience of handling and transportation which is not otherwise available. The extent of such concentration lies within the broad range of 0.40 to 40 percent sulfate ash, the range of concentration of 1.5 to 20 percent sulfate ash being preferred, however.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

I therefore particularly point out and distinctly claim as my invention:

1. The process of preparing oil-soluble alkaline earth metal sulfonates containing relatively large amounts of metal, which comprises the reaction of a neutral oilsoluble metal salt selected from the class consisting of alkaline earth metal and alkali metal salts of sulfonic acids, phosphorusand sulfur-containing acids derived from aliphatic polyolefins and a phosphorus sulfide, and phosphorus-containing acids derived from aliphatic polyolefins and phosphorus trichloride, with a sulfonating agent to form an acidic metal salt, and subsequent treatment of said acidic metal salt with a .stoichiometrically excessive amount of an inorganic basically reacting alkaline earth metal compound in the presence of a promoter selected from the class consisting of phenolic compounds and alcohols.

2. The process of claim 1 characterized further in that the product thereof is treated with carbon dioxide.

3. The process of claim 1 characterized further in that the neutral oil-soluble metal salt is a barium salt.

4. The process of claim 1 characterized further in that the sulfonating agent is chloro-sulfonic acid.

5. The process of preparing oil-soluble barium sulfonates containing relatively large amounts of barium, which comprises the reaction of a neutral oil-soluble barium salt selected from the class consisting of barium salts of sulfonic acids, phosphorusand sulfur-containing acids derived from aliphatic polyolefins and a phosphorus sulfide, and phosphorus-containing acids derived from aliphatic polyolefins and phosphorus trichloride, with chlorosulfonic acid to form an acidic barium salt, and subsequent treatment of said acidic barium salt with a stoichiometrically excessive amount of an inorganic, basically reacting barium compound in the presence of a promoter selected from the class consisting of phenolic compounds and alcohols.

6. The process of claim 5 characterized further in that the neutral oil-soluble barium salt is derived from a polyolefin-phosphorus pentasulfide condensation product.

7. The process of claim 5 characterized further in that the neutral oil-soluble barium salt is derived from the reaction product of a polyolefin, phosphorus trichloride and sulfur.

8. The process of claim 5 characterized further in that the neutral oil-soluble barium salt is the barium salt of a steam-treated reaction product of polyisobutylene, phosphorus trichloride and sulfur.

9. The process of claim 5 characterized further in that the promoter is a condensation product of an alkyl phenol and formaldehyde.

10. The process of preparing oil-soluble barium sulfonates containing relatively large amounts of barium which comprises the reaction of a neutral oil-soluble barium salt of an acid derived from the reaction of a substantially aliphatic polyolefin with phosphorus trichloride and sulfur, with chlorosulfonic acid to form an acidic barium salt and subsequent treatment of said acidic barium salt with a stoichiometrically excessive amount of an inorganic, basically reacting barium compound in the presence of an alkyl phenol, and treatment of this mass with carbon dioxide.

References Cited in the file of this patent UNITED STATES PATENTS 2,695,910 Asseff Nov. 30, 1954 2,767,164 Asseff Oct. 16, 1956 2,777,874 Assefi Jan. 15, 1957 

1. THE PROCESS OF PREPARING OIL-SOLUBLE ALKALINE EARTH METAL SULFONATES CONTAINING RELATIVELY LARGE AMOUNTS OF METAL, WHICH COMPRISES THE REACTION OF A NEUTRAL OILSOLUBLE METAL SALT SELECTED FROM THE CLASS CONSISTING OF ALKALINE EARTH METAL AND ALKALI METAL SALTS OF SULFONIC ACIDS, PHOSPHORUS- AND SULFUR-CONTAINING ACIDS DERIVED FROM ALIPHATIC POLYOLEFINS AND A PHOSPHORUS SULFIDE, AND PHOSPHORUS-CONTAINING ACIDS DERIVED FROM ALIPHATIC POLYOLEFINS AND PHOSPHORUS TRICHLORIDE, WITH A SULFONATING AGENT TO FORM AN ACIDIC METAL SALT, AND SUBSEQUENT TREATMENT OF SAID ACIDIC METAL SALT WITH A STOICHIOMETRICALLY EXCESSIVE AMOUNT OF AN INORGANIC BASICALLY REACTING ALKALINE EARTH METAL COMPOUND IN THE PRESENCE OF A PROMOTER SELECTED FROM THE CLASS CONSISTING OF PHENOLIC COMPOUNDS AND ALCOHOLS. 